Polymerizable compositions, including 4-allyloxymethyl-1, 3-dioxolane and polymerization products thereof



Patented June 24, 1952 UNITED STATES PATENT OFFICE POLYMERIZABLE COMPOSITIONS, IN-

CLUDIN G 4 ALLYLOXYMETHYL- 1,3

DIOXOLANE AND POLYMERIZATION PRODUCTS THEREOF No Drawing. Application August 10, 1950, Serial No. 178,756

13 Claims. (o1. zen-85.5)

This application is a continuation-in-part of our copending application Serial No. 106,974, filed July 26,1949, now Patent No. 2,578,861, issued December 18, 1951.

This invention relates to new polymerizable compositions, to polymerization products prepared therefrom and to methods of preparing such products. More particularly the present invention is directed to polymerizable compositions comprising (1) 4-allyl-oxymethyl- 1,3-dioxolane and (2) a compound which is difierent from the compound of (1) which is copolymerizable therewithand which contains a CH2=O grouping, e. g., styrene, acrylonitrile, ethyl acrylate, methyl methacrylate, etc., and to compositions comprising a copolymer of copolymerizable ingredients including as essential components the aforementioned compounds of (1) and (2). The scope of the invention also includes method features.

Many different vinyl and allyl compounds were known prior to our invention, but to the best of our knowledge and belief 4-allyloxymethyl-L3- dioxolane has not previously been prepared or used as a comonomer in the production of copolymers. The compound is unique in that it can be caused to polymerize either through its ethylenically unsaturated bond or through both the unsaturated linkage and the dioxolane ring. By suitable choice of catalysts, polymerization can be caused to take place primarily through the ring. Because of its unique structure and properties, the plastics chemist and resin formulator, and workers in related arts are provided with a single polymerizable material which, alone or preferably while admixed with another comonomer, can be caused to undergo either or both of two types of polymerization reactions as briefly described above. The advantages of such a polymerizable compound will be apparent to those skilled in the art, for example, the greater adaptability of such compounds for a greater variety of service applications by merely varying the catalyst or other polymerization influences employed, or the temperature or other polymerization conditions used, so as to direct the course of the polymerization through the ethylenic linkage and/or the dioxolane grouping as desired or as conditions may require.

As indicated above, 4-allyloxymethyl-l,3dioxolane is preferably caused to polymerize while admixed with one or more (e. g., two, three, five, ten, or any desired number) of other comonomers which are copolymerizable therewith, more particularly such comonomers which contain a CH2=G grouping (that is, comonomers which contain either a single CH2=C grouping or a plurality of such groupings), thereby to obtain copolymers, which in general are resinous or potentially resinous materials and which are especially valuable for use in the plastics, coating, laminating, adhesive, molding and other arts. Examples of comonomers with which this unsaturated dioxolane can be copolymerized are vinyl compounds, more particularly vinyl aromatic compounds (e. g., styrene, dimethyl styrene, divinyl benzene and other vinyl aromatic hydrocarbons) and vinyl aliphatic compounds, for instance acrylonitrile, acrylamide, the alkyl esters of acrylic acid (e. g., methyl, ethyl, propyl, etc., acrylates), the Various allyl esters, e. g., allyl acetate, diallyl .phthalate, diallyl succinate, etc.

It is an object of the present invention to provide a new class of polymerizable compositions containing 4-a1lyloxymethyl-L3-dioxolane and one or more other comonomers copolymerizable therewith, and a new class of copolymer compositions from the said polymerizable compositions.

Another object of the invention is to provide a new class of synthetic compositions, more particularly resinous copolymers, which are especially suitable for use in the plastics, coating, adhesive, laminating, molding and other arts.

Other objects of the invention will be apparent to those skilled in the art from the following more detailed description thereof.

In producing the polymerization products of our invention, 4-a1lyloxymethyl-L3edioxolane is preferably polymerized while admixed with a comonomer (or a plurality of comonomers) contaming one or more CH2=C groupings since, in general, products having optimum properties for a particular service use thereby can be obtained at minimum cost. Heat, light or heat and light can be used to effect polymerization, although under such conditions the rate of polymerizat1on is relatively slow. Hence, to accelerate the polymerization, we prefer to use a polymerization catalyst accompanied by heat, light or heat and l ght. Further details on polymerization conditions are given hereinafter.

Examples of monomers containing a CH2= grouping that can be copolymerized with the aforementioned unsaturated dioxolane, either s ngly or a plurality (two, three, four or any des red number) thereof, the latter often being deslrable in order to improve the compatibility and copolymerization characteristics of the mixture of monomers and to obtain new and valuable c0- polymers having the particular properties desired for a particular service application, are such 3 monomers as the unsaturated alcohol esters, more particularly the allyl, methallyl, crotyl, l-chloroallyl, 2-chloroallyl, cinnamyl, vinyl, methvinyl, 1- phenylallyl, butenyl, etc., esters of saturated and unsaturated, aliphatic and aromatic, monobasic and polybasic acids such, for instance, as acetic, propionic, butyric, valeric, caproic,.acrylic and alpha-substituted acrylic (including alkacry'lic, e. g., methacrylic, ethacrylic, propacrylic, eta, and arylacrylic, e. g., phenylacrylic, etc.), crotonic, oxalic, malonio, succinic, glutaric, adipic, pimelic, suberic, azelaic, sebacic, maleic, fumaric, citraconic, mesaconic, itaconic, acetylene di'carboxylic, aconitic, benzoic, phenylacetic, phth'alic, terephthalic, benzoylphthalic, etc., acids; the saturated monohydric alcohol esters, e. g., the methyl, ethyl, propyl, isopropyl, butyl, sec.-butyl, amyl, etc., esters of unsaturated aliphatic monobasic and polybasic acids, illustrative examples of which appear above; vinyl cyclic compounds (including menovinyl aromatic hydrocarbons), e. g., styrene, mand p-chlorostyrenes, -bromostyrenes, -fi1iorostyr'enes, -methylstyrenes, ethylstyrenes, -cyanostyrenes, the various poly-substituted styrenes such, for example, as the various di-, triand tetra-chlorostyrenes, -b'romostyrenes, fiuorostyrenes, -methylstyrenes, -ethylstyrenes, -cyanostyrenes, etc., vinyl naphthalene, vinylcyclohexane, vinyl furane, vinyl pyridine, vinyldibenz'ofuran, divinyl benzene, trivinyl benzene, allyl benzene, diallyl benzene, N vinyl carbaz'ole, the various allyl cyanostyrenes, the various alphasubstituted styrenes and alpha-substituted ringsubstituted styrenes, e. g., alpha-methyl styrene,

alpha-methyl-para methyl styrene, etc.; unsatu rated others, e. g., ethyl vinyl ether, diallyl ether, ethyl methallyl ether, etc. unsaturated amides, for instance N-allyl caprolactam, acrylamide, and N-substituted acrylamides, e, g, N meth'ylol acrylamida N-allyl acrylamide, N-methyl acryl= amide, N-phenyl acrylamide, etc.; unsaturated ketones, e. g., methyl vinyl ketone, methyl allyl ketone, etc.; methylene malonic esters, e. g., methylene methyl malonate, etc.; butadienes, e. g., 1,3-butadiene, 2'-chlorobutadiene, etc.; unsaturated polyhydric alcohol (e. g'., butenediol, etc.) esters of saturated and unsaturated, aliphatic and aromatic, monobasic and polybasic acids, illustrative examples of which appear above.

' polymerized with l-allyloxymethyl-lfi-dioiiolane are the vinyl halides, more particularly vinyl fluoride, vinyl chloride, vinyl bromide and vinyl iodide, and the various vinylidene compounds, including the vinylidene halides, e, g., vinylidene chloride, vinylidene bromide, vinylidene fluoride and vinylidene iodide, other comonomers bein added if needed in order to improve the compatibility and copolymerization characteristics of the mixed monomers.

Other and more specific examples of rhonomeric materials which may be mixed or blended with the unsaturated dioxol'ane used in practicing our invention and the resulting homogenethis or substantially homogeneous, pelymerizable composition then polymerized, as hereinafter more fully described, to yield new and vaiuame copolymer compositions are the allyl compounds which are difier'ent from the allyl coin'pcunq mbraced by Formula I and especially those which have a boiling point of at least about 60 C. Of the monomeric materials which may be used the allyl esters form a large class, all of which are suitable. The reactive allyl'compounds employed 4 are preferably those which have a high boiling point such, for example, as diallyl maleate, diallyl fumarate, diallyl phthalate, diallyl succinate, etc. Other allyl compounds which are not necessarily high boiling also may be used.

More specific examples of allyl compounds that can be copolymerized with 4-allyloxymethyl-L3- dioxolanev are. allyl alcohol, methallyl alcohol, allyl acetate, allyl methacrylate, diallyl carbonate, allyl lactate, allyl alpha-hydroxyisobutyrate, allyl trichlorosilane, allyl acrylate, diallyl malonate, diallyl oxalate,- diallyl gluconate, diallyl methylgluconate, diallyl adipate, diallyl azelate, diallyl sebacate, diallyl tartronate, diallyl tartrate, diallyl'mesaconate, diallyl citraconate, the diallyl ester of muconic acid, diallyl itaconate, diallyl chlorophthalate, diallyl dichlorosilane, the dia1lyl.ester of endomethylene tetrahydrophthalic anhydride, triallyl tricarballylate, triallyl aconitate, triallyl cyanurate, triallyl citrate, triallyl phosphate, trimethallyl phosphate, tetrallylvsilane, tetrallyl silicate, hexallyl disiloxane, etc. Otherexamples of allyl compounds-thatinaybe employed are given, for example,-in KropaPatent' No. 2,510,503, issued Junefi, 1950.

Among the comonomers which arepreferred for use in carrying our invention intoeffectare the vinyl compounds, including the vinyl aromatic compounds, more particularly the vinyl aromatic hydrocarbons (e. ghstyrene, isopropenyl toluene; the various dialkyl styrenes, etc:), and the vinyl aliphatic compounds, e.- g., acrylonitrile, acryl+ amide, etc., and other compounds containingia CHz' '-G grouping, e. g., the various-substituted acrylonitriles (e. g., methaerylonitrile, ethacrylo nitrile, phenylacrylonitrile, etc), the various substituted acrylamides (e.- g., methacrylamide; th acrylamide, the various N-substituted acryls amides and alkacrylamides, for instance N methylol acrylamide, N-monoalkyl and dialkyl acrylamides and-methacrylamides, e. g.-, N-mono'- methyl, -ethyl, -propyl, -butyl, etc and N-di methyl, -ethyl, -propyl, gbutyl, etc., acrylamide's and methacrylamides, N-monoaryl and =dia'ryl acrylamides and alkacrylamides, e. g., N mono phenyl and -diphenyl acrylainidesand moth acrylamides, etc), vinyl esters, e; g., vinyl ace tate, vinyl propionate, vinyl 'buty'rate, vm nsm butyrate, vinyl valerate, vinyl acrylate, v'in'yl methacrylate,- 'etc., esters of an acrylic acid (in eluding acrylic acid itself and the various alpha-'- substituted acrylic acids, e. g., inethacrylic-acid, ethacrylic acid, phenylacrylic acid, etc). more particularly the alkyl'esters'of anaerylic'acid, e. g., the methyl, ethyl, propyl, isopropyl, n=biityl, isobutyl, sec.b'ut'yl, tert-.butyl, amyl, hxyl, heptyl, octyl, decyl, dodecyl, etc.-,- esters bf acrylic,- methacrylic, ethacrylic, phenylae'rylic, etc., acids, including the alkyl acrylates'contaim me not more than'four carbon atoms in the ester grouping, examples of which are given'abov'e, as well as other vinyl aromatic and vinyl aliphatic compounds, and other compounds containing a CH2=C grouping;

Any suitable means may be used in effecting polymerization of a polymerizable composition containing 4-allyloxymethyl-1,3-dioxolahand one or more other monomers which are coptily merizabletherewith; Heat or lightor both, with or without a polymerization catalyst, can'be-used. Ultraviolet light is moreefiective than ordinary light; Preferably a polymerization catalyst is employed. Any of the catalysts which-arouseful in accelerating the polymerization of coinpounds containing an ethylenically unsatifiatd mer or mixture of monomers.

grouping, specifically a vinyl grouping, can be used. Among the preferred catalysts are: the

acidic peroxides, e. g., benzoyl peroxide, phthalic peroxide, succinic peroxide and benzoyl acetic peroxide, as well as fatty oil acid peroxides, e. g., coconut oil acid peroxides, lauric peroxide, stearic peroxide and oleic peroxide; alcoholic peroxides, e. g., tert.-buty1 hydroperoxide; and terpene oxides, e. g., ascaridole. Other examples of organic peroxide catalysts that can be employed are the following:

I Tetralin hydroperoxlde Tert.-butyl diperphthalate Cumene hydroperoxide Tert.-butyl perbenzoate Acetyl peroxide 2,4-dichlorobenzoyl peroxide Urea peroxide C'aprylyl peroxide 'p-Clhlorobenzoyl peroxide 2,2'-bis(di-tert.butyl peroxy) butane Hydroxyheptyl peroxide Diperoxide of benzaldehyde Examples of catalysts which are believed to accelerate polymerization primarily by opening up the dioxolane ring and, also, may cause polymerization to proceed through the ethylenically unsaturated grouping are: p-toluene sulfonic acid, sulfuric acid, phosphoric acid, aluminum chloride, stannic chloride, ferric chloride, boron trifiuoride-ethyl ether complex, iodine, etc. Certain alkaline catalysts also seem to function in a similar manner, e. g., ethylene diamine, tetraethylenepentamine, etc.

Catalysts which accelerate polymerization as 1 the result of the liberation of a free radical, e. g., sym-dicyanotetramethylazomethane and similar known diazo polymerization catalysts, also can be employed.

If desired, partial polymerization of the unsaturated dioxolane can be effected with the aid 1 of one polymerization catalyst (e. g., a peroxide and, more particularly, an organic peroxide catalyst, or with a diazo or other type of catalyst capable of liberating a free radical) and polymerization then completed with the aid of a catalyst capable of opening up the dioxolane ring, e. g., stannic chloride, etc.

The concentration of catalyst is relatively small, e..g., from, by weight, about 1 part of catalyst per thousand parts of the mixture of monomers to be polymerized to about 3 or 4 or more parts of catalyst per hundred parts of the mono- If an inhibitor be present in the polymerizable composition, up to '6 or 7% or even more, based on the weight of the said composition, may be necessary (according to the concentration of the inhibitor) in order to overcome the effect of the inhibitor and to cause polymerization to proceed as desired within a reasonable period of time.

The proportions of 4-ally1oxymethyl-1,3-dioxolane and monomeric material which-is copolylane to from 9'? (about 97) to 3 (about 3), or

lower, molar percent of the other comonomer. Preferably the unsaturated dioxolane constitutes at least 5 molar percent of the mixture thereof with the other comonomer or mixture of comonomers. When the comonomer. constitutes only about 3 molar percent by weight of the polymerizable composition and the unsaturated dioxolane constitutes the remainder, the changes in the properties of the polymerization product are less marked (as compared with the homopolymeric dioxolane) than when the comonomer (or mixture of comonomers) constitutes a substantially larger amount, as for example 10 or 20 molar percent or even as much as 30 or 40 molar percent of the polymerizable composition. Particularly valuable copolymer compositions are obtained by using, by weight, from 10 to 5 0 molar percent of the unsaturated dioxolane and from to 50 molar percent of a comonomer (or mixture of comonomers) which is copolymeri'zable therewith and which contains a CH2=C grouping, numerous examples of which have been given hereinbefore. I In some cases it may be desirable to incorporate into the polymerizable composition (especially those comprising the unsaturated dioxolane and one or more comonomers) an inhibitor which is adapted to inhibit polymerization through the ethylenically unsaturated grouping of the monomeric material. When it is desired to use the inhibitor-modified composition, a catalyst is added in an amount s'ufiicient to promote the polymerization reaction. Various inhibitors can be used for this purpose, e. g., pheny -a naphthylamine, N,N-di-2-naphthyl-p-phenylenediamine, certain cupric salts, e. g., cupric acetate, etc. The amount of inhibitor may be considerably varied but ordinarily it is employed in an amount not exceeding 3%, generally less than 1%, by weight of the polymerizable composition, e. g., from 0.01% to 0.5% or 0.6% by weight of the said composition.

The polymerization may be effected by conven- "tional bulk polymerization technique, in the saturated dioxolane and one or more other comonomers, to which has been added a small amount of suitable polymerization catalyst, may be caused to polymerize to yield a copolymer or interpolymer by passage through a conduit with alternate hot and cool zones.

The temperature of polymerization of the polymerizable composition, at atmospheric or slightly above atmospheric pressure and in the presence or absence of a polymerization catalyst, may'be varied over a wide range, up to and including or slightly above the boiling point at atmospheric pressure of the mixture of monomers. In most cases the polymerization temperature will be within the range of 15 to 200 0., more particularly within the range of 20 C. or 30 C. (ordinary room temperature) to -140 0., depending, for example, upon the rapidity of copolymerization wanted, the particular catalyst, if any, used, the particular mixture of comonomers employed when a particular copolymer is wanted, and other influencing factors. With certain polymerization catalysts, more particularly strong acidic polymerization catalysts such, for instance, as gaseous boron trifluoride, boron trifluoride-ethyl ether complex, concentrated sulfuric acid, anhydrous aluminum chloride, etc., a substantially lower polymerization temperature often advantageously can be used, e. g., temperaum; V'iseOusGolutioncontain-lug a copolyrner of "e'myl am-91am fand theaforementioned dioxolane normal temp ratures in film or bulk form. open Iri'bidiiftht thoseslilldinithe itjbtter mey understafid how the l present invention eein' be be led intdefi'ect; thefo llow'in'g xamples are fgire'n' by "waver illustration aridnot'liy 'wayof' Amman-er the abet/e ingredients is heated a or 1 hour, 'Aft'er distilling 011 mm;- 'water arid exEe'ss' fermhae yae from the 'resulti-iig redt'iofl'ma'ss, the residue is neutraliked:Withjtri- "ethaholaniir'ie and thereafter washed with water.-

Distillation is continfieduntil-no moredistillate is? obtained at ajbathternperature' of 1'15" (3. The

"'ai'exolafie' is "colleotediasthe" product t n ng at ia yi'eld 'amoiiiitiii'gftoj" about 29 "It 'is' a 1ear,--mobi1e, eolor'lss liquid; 115 1.4401.

5 T EXAMPLE 2 "Y'arts allyloxymethyi-ifi -diokola'i1e 1 .0 i 'Ethyracrylate 10.0 "Benzene "20.0 Benzoyl peroxide 0.2

e he'etedtogethefuriderfrefiux at the' h'oiling ip'rature of them'a'ss 'for 5*h'ours. Theresult- 5 In'steadbf ethyl acrylate ather eonioriemers,

"more partieularly other esters 0f -acrylic a'eid, e. *=g., methy1"'flrylateflprepyl aeiylalte, isepeepyl -eLerylate,'- n butyl aorylate,-dsebutyl-acrylatefisee- "bum aerylate tertz-butyl aerylatej-amyl a'eiylete, lo hecyl aiylate, pre nyleeerylate, oyeloheiyl acrylate, phenyl acrylate, lieriz'yl a'e'rirlate, em, can be substituted in the aboveformulatien thereby to obtain copolymer oompositions of varying properties. As withethyl 'acrylate-sd too with such other comonomers theproportionsof components can be varied as 'desire d dr ascenditions may require, e.=; g., from 3-to 7mn-higher) molar percent of the dioxolane' to from 97 150 3' (or lower) molar percent of the other cbmcmemer.

''20 Preferably the comonomerconstitute's' frame-'10 to 95-90 molar percent of the mixturethereof with the dioxolane.

are ehargedto a 3-neck'ed reaction vesserequlpped with a'st'irrer arid-e; refiuxeona'enser. 'me mixture is stirred vigorously whilemeatirig -oma; steam bath for'9fl' minutesfat the end of wh h period -"reflu'JZi-ng has eeaeed. ste'am- :new passed '-'th-roi 1gh' theemiilsien for li minutes to remove residual-monomers. -A sn'iall am'ount of co- 40 agulated copolymer is filtered outof the' 'stame emulsion of i the c'opo'lymer': of 'styrene' -and the aforementioned --"unsatui ate d' dioxolane.

-The c'opolymer la't'ex' may be -u'sed as a coating composition or as a' component; ofshc'h composimm. For ex'ample; it may be applied to stemface of glass, metal; wood or other' materialto 'be protectively finished, and-the coated 'article then heated for from 1 to 3'h0urs ata teinperatilre of the order of 120 C; to140-CJto evaporateRhe Water and to convert the reactive :stymne-un- *saturated dioxolane cop'olymer to a cured unsub- 's' tar rtially insoluble substantially "infuslble state. 'The co fi'olzymermay be! precipitated; if deslred, from the aqueous emulsion thereof by adding a coagulating -agent" such; for instance; 'as salts (e5 T g.," fsa1ts- 0f polyvalent metals such asialumi- 7 Sulfate, magnesium chlorideg' bari'um chloride; etc salts of mon'ovalent metals :such 'as sodlum' chloride; sodium sulfate," etc.) a'cids 21g 1 polymerizationcatalystor other modifyi'ngm' ent,

'm'ay be molded under 'heatand pressurwe. gei flt 1 =140"-'C. to 1 10 02 and undene pressuresofi- 0 m are heated together under reflux at the boiling temperature of the mass for 5 hours. From the resulting mass a solid copolymer of acrylonitrile and 4-allyloxymethyl-1,3-dioxolane can be isolated by evaporating or distilling off the benzene.

EXAMPLE Parts Ethyl acrylate 90 4-allyloxymethyl-1,3-dioxolane are dissolved together, and the resulting solution is then added to Parts Sodium lauryl sulfate 1.5 Ammonium persulfate 0.5 Deionized water 300.0

The resulting mixture is heated with stirring in a reaction vessel placed on a steam bath for 1 /2 hours, after which stirring is stopped, and steam is passed rapidly through the mass for minutes in orderto remove unreacted monomers. The steamed emulsion is cooled and strained to remove lumps of coagulated copolymer. A portion of the emulsion is diluted with water to 10% solids and is used to impregnate woolen fabrics. The impregnated cloth is dried for 10 minutes at 300 F. and is tested for shrinkage after being given five successive standard washings in a soap solution. The treated wool shrinks about 10%, whereas the untreated wool shrinks about 17%.

Similar results are obtained when 5 parts of 4- allyl-1,3-dioxolane and 5 parts of 4-allyloxymethyl1,3-,dioxolane are substituted for 10 parts of 4-ally1oxymethyl-1,3-dioxolane in the above formula. I

EXAMPLES Parts Methyl acrylate 45.0 Ethyl acrylate 45.0 4-allyloxymethyl-1,3-dioxolane 10.0 v 25% solution of dioctyl sodium sulfosuccinate in water 20.0

coating composition or as a component of such compositions. 7

EXAMPLE 7 Parts Methyl methacrylate 50 4-allyloxymethyl-1,3-dioxolane 1 50 Benzoyl peroxide 1 are mixed together and charged to a heavywalled glass tube, which thereafter is sealed under vacuum. Copolymerization is eifected by heating the sealed tube in a 60 C. Water bath for 24 hours. A hard copolymer of methyl methacrylate and 4-allyloxymethyl-' lgs-dioxola'ne' obtained;

10 EXAMPLE 8 Parts Ethyl acrylate 10.0 4-allyloxymethyl-1,3-dioxolane 10.0 Toluene 20.0 Benzoyl peroxide 0.2

are heated together under reflux at the boiling temperature of the mass for 5 hours. The yield of copolymer solids is 28.6%, which corresponds to 57.2% conversion of monomers to copolymer. Clear'films are obtained by casting thesolution on glass plates and baking as described in, the preceding example.

EXAMPLE 9 Parts 4-allyloxymethyl-L3-dioxolane 10.0 Styrene 10.0 Xylene 20.0 2,2-bis(di-tert.-butyl peroxy) butane 0.2

are heated together under reflux at the boiling temperature of the mass for 5 hours, yielding a homogeneous, slightly viscous solution of the copolymer of the unsaturated dioxolane and styrene. Films dried from the xylene solution are clear and tough.- Their solvent resistance can be indiamine, tetraethylenepentamine, etc., into the copolymer solution prior to drying.

EXAMPLE 10 Parts Acrylonitrile x 100.0 4-allyloxymethyl-1,3-dioxolane 100.0 25% solution of dioctyl sodium sulfosuccinate 24.4 Water 574.0 30% aqueous solution of hydrogen peroxide- 4,4

All of the above ingredients with the exception of one-half (2.2 parts) of the aqueous hydrogen peroxide solution are charged to a reaction vessel as described under Example 3. The mixture is stirred vigorously while heating under reflux on a steam bath for 1% hours, after which the remainder (2.2 parts) of the aqueous hydrogen peroxide solution is added to the reaction mass.

cake of copolymer is washed with water and dried in a vacuum oven at 50 C. for 48 hours, yielding a dried, reactive copolymer of acrylonitrile and 4- ally1oxymethyl-1,3-dioxolane. polymer, alone or admixed with a filler, polymerization catalyst or other additive, is adapted. to-

be molded under heat and pressure to yield molded articles of various shapes.

EXAMPLE 11 This example illustrates the production of copolymersof acrylonitrile and 4-allyloxymethyl- 1,3-dioxolane, using from 5 to molar percent of the one to from 95 to 5. molar percent of the other, and benzoyl peroxide as a catalyst for the copolymerization reaction. The ingredients. were About 60 parts of concentrated hydro' This reactive co- 1t mixed together andcharged: to heavy-walled glasstubes, which thereafter were evacuated and sealedunder vacuum. Copolymerizatiomwasnfis i'ected' by heating the, sealed, tubes. ina. 6.0? 0.:

water bath for 120 hours. The proportionsused and; results obtained" are tabulated below:

Table.

Benzoyl. Ap meetiremade Parts Molaper cent Mole Parts per cent prised mainly w t ranularsolid'. .Some,

brownish, rub;

. was present:

. Do. 'Product'co'mprised mainly a homogene- OHS; rubbery solid.

The= copol'ymer was; obtainedviscous, brownish liquid;

Itwill be. understood, of course, by. thoseskilled intheart that our invention. is not. limitedto the specific ingredients named in the. above illustrative examples nor to the particular proportions and methods of polymerization and copolymerization mentioned therein. Thus, instead of benzoyl peroxide and the other catalysts named in the different examples, any. other. polymerization catalyst or combination. of polymerization. catalysts, numerous examples of which havebeen giventhereinbefore, may be used. Other catalysts that can be employedare other salts of per-acids,

e. g., sodium and potassium persulfates, sodium and. potassium. percarbonates; sodium: and potassium per-borates, sodium and: potassium per-phosphams, etc. Also, instead! of using 4=a1lyloKitmethyl-1,3: -dioxolane and the other-,comonomer orcomonomersy in' the particular proportions givenv in' the-various. examples; they can. be used in. other proportions, for instance-in the proportionsimetni'oned by Way ofulllustrationinthepor tionof: the specificationiprior to the-examples, and also: under Example .2 with particular referencetonnrylate comonomers.

A comonomer (or plurality of: comonomers) which contain one or more CH2=C; groupings, which is different from theunsaturatedzdioxolane and which. is compatible and. copolymerizable therewith, other than. the particular comonomers given in the above illustrative examples, also can be used. For instance,the comonomer may-be a cyanoalkyl ester of an acrylic acid, e. g., mono-, d-iand tricya-nomethylzesters of acrylic acid, methacrylic acid, etc., the mono.-, di-. and, tri- (fl oyanoethyl) estersof acrylic acid, methacrylic acid; etc- Or, the comonomer can be any other organic compound which is. copolymerizable-with the unsaturated dioxolane and which .is repwhere, R represents a member of the class con-- sisting' of: hydrogen, halogen (chlorine, fluorine,

Gopolymerization. D -Uct 1 1 as a somewhat 123 bromine or iodine), alkylfle gz, methyl, ethyl, propyl, butyl to octadecyl, inclusive), vcycloall-ryl phenyl, etc.), aralkyl (e. g., benzyl', phenyl'ethyl, etc.) and R. represents an aryl radicalor. agradt-m cal represented by the formula where R" represents n lkvhalk xr lkvl ere-J;

meth xvmethyll methoxyet y th xsethyl, ethoxypropyl, propoxybutyl, etc.) or a carbocyclic radical (e. g:, aryL alkaryI; hydroarom'atic etc). Examples of compounds embraced by-Formu-la. II areithe vinyl esters (e: g., vinyl acetate, etc-i), methyl vinyl ketone, isoprene, LZi-butadiene, 2 chIQro-LB-butadiene, acryl'onitrile various esters of acrylicacid (e. g., methylacrylate, ethyl acrya late, cyclohexy-l acrylate, tetrahydronaphthyrace.

rylate, decahydronaphthyl acrylalte, methoxy ethyl acrylate, ethoxyethylacrylate, etc), as wellas others that will be obviousto those. skilled the art.

The thermosetting or-potentiallythermosetting, reactive polymerization products- (polymersand. copolymers) ofthis invention havea wide variety of applications. For instance, with or without a filler or other additive, numerous examples of which have been hereinbefore, theymay beused as molding compositions (or as components on molding compositions) from which molded ar-. ticles are produced by" molding; the composition under heat and pressure, e. g., at temperatures oftheorder of to 200 C. and under pressures ranging between 1 000 and 10,000 pounds,

square inch. Among the fillers. that can be; em.-. ployed in the production. of molding: compositions.

are alpha-cellulose pulp, asbestos fibers, cotton flock, chopped cloth cuttings, glass fibers, wood flour, antimony oxide, titanium dioxide, sand, clay, mica dust, .diatomaceous earth, etc.

The liquid, p ly er zable compositions, f, ou in ention a so an be. used in, the roduct on o castings; as adhesives, for instance in th production of optical v ces tain ng, a plu ality f l ments, w impl sv i which, are, comp und ns s, mp d prisms, ol pr s s, n t tr atmento p er r. P per s o amiqfpr v rious her purp s We claim:

1. A polymerizable composition comprising ('1) 4-allyloxymethyl-L3-dioxolane and (2) a compound which is copolymerizable with the compound of (1) and which is representedby the general formula Gilead where R represents a member of theaclass-con aryl, alkaryl and iaralk-yl radicals, and. hfcrepre-n 13 sents a radical of the class consisting of an aryl radical and radicals represented by the formulas where R" represents a radical of the class consisting of alkyl, alkoxyalkyl and canbocyclic radicals, the ingredients of (1) and (2) being present in the said polymerizable composition in the ratio of from 3 to 97 molar percent of the former to form 97 to 3 molar percent of the latter.

2. A polymerizable composition as in claim 1 wherein R in the formula for the compound of (2) is hydrogen.

3. A polymerizable composition as in claim 1 wherein the compound of (2) is acrylonitrile.

4. A composition comprising a copolymer of copolymerizable ingredients including (1) 4- allyloxymethyl-1,3-dioxolane and (2) a compound which is copolymerizable with the compound of (1) and which is represented by the general formula where R represents a member of the class consisting of hydrogen, halogen, and alkyl, cycloalkyl, aryl, alkaryl and aralkyl radicals, and R represents a radical of the class consisting of an aryl radical and radicals represented by the formulas where R" represents a radical of the class consisting of alkyl, alkoxyalkyl and carbocyclic radicals, the ingredients of (l) and (2) being present in the polymerizable composition in the ratio of from 3 to 97 molar percent of the former to from 97 to 3 molar percent of the latter.

5. A composition as in claim 4 wherein R in the formula for the compound of (2) is hydrogen.

6. A composition as in claim 4 wherein the compound of (2) is acrylonitrile.

7. A composition as in claim 4 wherein the compound of (2) is an alkyl ester of acrylic acid.

8. A composition as in claim 7 wherein the alkyl ester of acrylic acid is ethyl acrylate.

9. A composition as in claim 4 wherein the compound of (2) is an alkyl ester of methacrylic acid.

10. A composition as in claim 9 wherein the alkyl ester of methacrylic acid is methyl methacrylate.

11. The method of preparing a new synthetic composition which comprises polymerizing under heat, while admixed with a. polymerization catalyst, a pclymeriza'lale composition comprising (1) 4-allyloxymethyl-1,3-dioxolane and. (2) a compound which is copolymerizable with the compound of (l) and which is represented .by the general formula CH G Where R represents a member or the class consisting of hydrogen, halogen, and alkyl, cycloalkyl, aryl, alkaryl and aralkyl radicals, and R represents a radical of the class consisting of an aryl radical and radicals represented by the formulas REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Name Date Reppe Nov. 2, 1937 Number 

1. A POLYMERIZABLE COMPOSITION COMPRISING (1) 4-ALLYLOXYMETHYL-1,3-DIOXOLANE AND (2) A COMPOUND WHICH IS COPOLYMERIZABLE WITH THE COMPOUND OF (1) AND WHICH IS REPRESENTED BY THE GENERAL FORMULA 